Subresinous polyesters



Patented Nov. 12, 1946 1 snaltnsrsoos POLYESTERS Melvin De Groote,University City, and Bernhard Keiser, Webster Groves, Mo., assignors toPetrolite Corporation, Ltd., Wilmington, DeL,

' a corporation of Delaware No Drawing. Original application March 3,1943,

Serial No. 478,597. Divided and this application September 2, 1943,Serial No. 501,031

6 Claims. (Cl. 260404.8)

This invention relates to a new composition of matter, our presentapplication being a. division 01' our pending application Serial No.478,597, Patent No. 2,385,970, filed March 3, 1943.

The main object of ourinvention is to provide a new material orcomposition of matter, that is particularly adapted for use as ademulsifier in the resolution of crude oil emulsions, but which is alsoadapted for use in other arts, as hereinafter indicated. For instance,the said material may a novel method for producing said new material orcomposition of matter.

The new material or composition of matter herein described, consists ofa fractional ester, i. e., an ester containing at least one freecarboxylic radical, and containing radicals, or groups derived from thefollowing reactants:

(a) A polybasic carboxy acid;

(b) A high molal detergent-forming monocarboxyacid;

(c) A member of the class consisting of oxyacyclic alkanes andcycloalkanes. The preparation of such hydroxylated bodies for subsequentreaction with phthalic 'anhydride or the like is well known. Forconvenience, reference is made to U. S. Patent No. 2,240,472, datedApril 29, 1941, to Swan. The subject-matter following immediately is inessentially verbatim form, as it appears in said aforementioned Swanpatent. 'I'hus, one class of raw materials includes the di-(polyalkyleneglycoxy) alkanes in which the alkenyl radical is selected from the groupconsisting of the aliphatic alkenyl radicals containing from 8 to 18carbon atoms and the dlcyclohexenyl diaikyl methanes, in which eachalkyl radical contains less than 3 carbon atoms, each polyalkyleneglycoxy chain contains from 5 to 20 alkylene glycol radicals, and thealkylene radical is selected from the group consisting of ethylene andpropylene.

The di- (polyalkylene glycoxy) alkanes, in which the alkenyl radical ian aliphatic alkenyl radical of from 8 to 18 carbon atoms, e. g.,rli-(polyethylene glycoxy) decane noomcmm.cntonoro.(cHo e.(cmomcnomomoamay be prepared in a manner similar to that shown in British Patent No.443,559, by condensing ethylene oxide or propylene oxide with dihydricalcohols of from 8 to 18 carbon atoms,

0 e. g., decamethylene glycol.

clan-cm The di- (polyalkylene glycoxy) alkanes in which the alken'ylradical is a di-cyclohexenyl dialkyl methane, e. g.,4:4'-di'-(polyethylene glycoxycyclohexylldimethyl methane CH: Clix-OH:-

CHr-CH: en. cHr-c I alkylated pohrhydric phenols, di(polyalkylene 4 maybe prepared as follows: Phenol is reacted glycoxy) alkanes, in which thealkenyl radical is selected from the group consisting of the aliphaticalkenyl radicals containing from 8 to 18 carbon atoms; and thedi-cyclohe'xenyl dialkyl methanes in which each alkyl radical containspreferably less than 10 carbon atoms; and

(d) A polyhydric alcohol radical as a linking radical wherever required.

Although the cycloaliphatic compounds, i. e., cycloalkanes, are notnecessarily the obvious equivalent of the acyclic alkanes, we have foundthat no differentiation need be employed in respect to the compositionsherein contemplated. The word alkane," unless indicated otherwise, willbe employed in its broadest aspect to include compound). This compoundis hydrogenated as with acetone (or diethyl ketone or methyl ethylketone), as described in U. S. Patent No. 1,225,748. of Wallace A.Beatty, to give the compound diphenylol dimethyl methane.

1 c v C csHioH (or the corresponding diethyl or methyl ethyl describedin British Patent. No. 274,439,' to'"give the correspondingdicyclohexylol dialkyl methane. This is then condensed with ethyleneoxide or propylene oxide, in a manner similar to that shown in BritishPatentNo. 443,559. Such compounds are mentioned in French Patent No.772,302. It is to be noted, however, that the raw materials employed inthe present instance for reaction with phthalic anhydride or the like,are

not limited to those which are especially watersoluble but include thoseof lesser water-solubility than the type described in said Swan patent.For this reason, one is not limited to the use of ethylene oxide andpropylene oxide as a reactant, but may employ other compounds having areactive ethylene oxide ring.

As typical examples of applicable compounds may be mentioned glycerineepichlorhydrin, glycid alcohol, ethylene oxide, propylene oxide,butene-2-oxide butene-l-oxide, isobutylene oxide, butadiene oxide,butadiene dioxide, chloroprene oxide, isoprene oxide, decene oxide,styrene oxide, cyclohexylene oxide, cyclopentene oxide, etc. In actualuse we have found that one can obtain the cycloalkane derivatives morecheaply and more readily than the acyclic derivatives. In other words,straight chain or branched chain dihydric alcohols containing from 8 to18 carbon atoms or thereabouts, are comparatively expensive, whereas,certain phenol-ketone condensation products, known generically in theart as bis-phenols are readily available and are comparativelyinexpensive. As to'the manufacture of bis-phenols, reference is made toU. S. Patent No. 2,182,308, dated December 5, 1939, to Britton andBryner. Bis-phenols have the general formula:

HO-R

wherein R is an aryl group and the free bonds are linked with alkylgroups or an alkylene radical. They are commonly prepared by reacting aphenol, e. g., phenol, o-cresol, etc., with a ketone such as acetone,methyl-ethyl-ketone, dibenzyl ketone, cyclohexanone, etc., in thepresence of a concentrated strong mineral acid such as sulfuric orhydrochloric acid. Any ketone, e. g., acetone, methyl ethyl ketone,diethyl ketone, dibutyl ketone, cyclohexanone, may be employed in thereaction and also a variety of phenols can be used; for instance,phenol, o-cresol, o-chlorphenol, etc., are suitable.

Similar reagents are derivable from a variety of othercarbonyl-containing compounds, including ketones, in which the carbonyloxygen is activated by the presence of a halogen as a substituent for ahydrogen atom, alpha-chlorinated aldehydes, etc. In the art relating tothis type of compound they are sometimes described as substitutedmethanes; other times as substituted 2,2 propanes. Although there isextensive literature dealing with this type of compound, reference ismade only to a few additional patents, to wit: British Patent No.274,439, -to Chemische Fabrick Auf Action; to British Patent No.254,753, referred to previously, and British Patent N0. 443,559 to I. GFarbenindustrie, A. G. Alcohols obtained from ricinoleic acid,hydroxylated ricinoleic acid, etc., in which the two hydroxyl radicalsare separated by at least 8 carbon atoms, are also satisfactory asreactants of the acyclic type. It is to be noted that such glycols aretreated with oxyalkylating agents in the manner described in thetreatment of cetyl alcohol, in Example 1 of the aforementioned BritishPatent No. 443,559.

Although it is not believed that a further d scription is required inrespect to glycols or hydroxylated compounds employed as reactants, thefollowing may be included by way of illustration: It may be well toemphasize that when glycid or the equivalent is employed, either aloneor in combination with ethylene oxide, one may obtain a reactant whichcontains more than two alcoholic hydroxyls, and thus, in the strictestsense of the word, is not a glycol, but is conveniently included in thepresent instance and is contemplated within the scope of the heretoattached claims.

HYDROPHILE HYDROXYLATED ALKANES Example 1 1 pound mole of decamethyleneglycol is condensed with 6 moles of ethylene oxide.

HYDROPHILE HYDROXYLATED ALKANES Example 2 The same procedure isfollowed, except that 12 moles of ethylene oxide are employed.

HYDROPHILE HYDROXYLATED ALKANES Example 3 The same procedure isfollowed, except that 18 moles of ethylene oxide are employed.

HYDROPHILE Hxnnomsran ALI-mus The same procedure is followed as inExamples 1 to 4, preceding, except that ricinoleyl alcoholdi(hydroxy)octadecene is substituted for decamethylene glycol, in thepreceding examples.

Hrnaormu: HYnRox'YLArnn Amunrs Example 6 The alcohol derived fromhydrogenated castor oil, a hydroxystearic acid glyceride, and sometimesreferred to as di(hydroxy)octadecane, is substituted for decamethyleneglycol, in the preceding Examples 1 to 4.

HYnxoPmLr: HYnaox'YLA'ren ALxANss Example 7 Needless to say, the sameprocedure for producing glycol or polyglycol ethers of polyhydricalcohols applies with equal force and effect to the polyhydric phenols.The manufacture of these compounds is well known, and for a completedescription see British Patent No. 470,181, to.I. G. Farbenindustrie, A.G. Attention is called particularly to certain suitable phenolic rawmaterials mentioned in said aforementioned British patent.

Such polyhydric phenols include isononyl resorcinols. Note,particularly, Example 14 of said British patent, which is concerned withoxyethylated iso-octyl resoreinol. Due to its availability, weparticularly, prefer compounds obtained by treating 4-tert-butylcatechol (4-tert butyl-1,2-dihydroxy-benzene) with low molal alkylatingagents, such as ethylene oxide, propylene oxide, butylene oxide, glycid,

HYDROPHILE HYDROXYLATED POLYHYDRIC PHENOLS Example 1 1 pound mole ofmixed isononyl resorcinols is treated with 6 moles of ethylene oxide.(See aforementioned British Patent No. 470,181.)

I HYDROPHILE HYDROXYLATED POLYHYDRIC PHEN OLS Example 2 1 pound mole ofiso-octyl resorcinol is treated with 6 moles of ethylene oxide. (Example14 of aforementioned British Patent No. 470,181.)

HYDROPHILE HYDROXYLATED POLYHYDRIC PHENOLS Example 3 1 pound mole of4-tert-butyl catechol is treated with 6 moles of ethylene oxide.

HYDROPHILE HYDROXYLATED POLYHYDRIC PHENOLS Example 4 1 pound mole of(dihydroxy phenyl) -dimethylmethane is treated with 6 moles of ethyleneoxide. '1'

HYDROPHILE HYDROXYLATED POLYHYDRIC PHENOLS I Example 5 1 1 pound mole ofdi(4-hydroxy toluyl) -dimethyl-methane, obtained from acetone and orthocresol instead of acetone and phenol, is treated with 6 pound moles ofethylene oxide.

HYDROPHILE HYDROXYLATED POLYHYDRIC PHENOLS Example 6 The same procedureis followed as in Examples 1 "1 to 5, preceding, except that 12 moles ofethylene oxide are employed instead of 6 moles. HYDROPI-IILEHYDROXYLATED POLYHYDRIC PHENOLS Example 7 The same procedure is followedas in Examples 1 to 5, preceding, except that 18 moles of ethylene oxideinstead of 6 moles of ethylene oxide are employed.

HYDROPHILE HYDROXYLATED POLYHYDRIC PHENOLS Example 8 equivalents, suchas the anhydrides, esters, or acyl chlorides, may be employed. Amongvarious available polybasic carboxy acids suitable for use as reactants,are citric acid, tartaric acid, oxalic acid, phthallc acid, maleic acid,malic acid, succinic acid, adiplc acid, azaleic acid, fumaric acid,citraconic acid, etc. We particularly prefer to use the dibasic acids.It is to be noted that numerous examples are available as anhydrides,rather than acid. Reference is made specifically to phthalic anhydride,maleic anhydride, citraconic anhydride, etc.

The detergent-forming monocarboxy acids containing at least 8 and notmore than 32 carbon atoms, are characterized by the fact that theycombine with alkalies to produce soap or soaplike materials. Thesedetergent-forming acids include fatty acids, resin acids, petroleumacids, etc. For the sake of convenience, these acids will be indicatedby the formula R.COOH. Certain derivatives of detergent-fanning acidsreact with alkali to produce soap or soap-like materials, and are theobvious equivalent of the unchanged or unmodified detergent-formingacids; for instance, instead of fatty acids, one might employ thechicrinated fatty acids. Instead of the resin acids, one might employthe hydrogenated resin acids. Instead of naphthenic acids, one mightemploy brominated naphthenic acids, etc. Acids obtained by the oxidationof petroleum fractions or waxes may be employed. This type of acid mayalso be subjected to various modifications, provided such modificationsstill retain detergentforming properties.

A description of polyhydric alcohols is not necessary, since theyrepresent a common class of chemical compounds. It is to be noted,however, that ,polyhydric alcohols are understood to include the ethertype, such as diethylene glycol, triethylene glycol, tetraethlyleneglycol, etc., as well as cyclic and acyclic polyglycerols, includingdi-glycerol, tri-glycerol, etc. Common examples include glycerolethylene glycol, propylene glycol, etc.

In contemplating suitable procedurefor forming the acidic esters hereincontemplated, it is to be noted that a detergent-forming monocarboxyacid radical must be present. Such detergentforming monocarboxy acidcompound may or may not have a hydroxyl radical present. For instance,ricinoleic acid, hydroxystearic acid, dihydroxystearic acid, and thelike, would have an alcoholic hydroxyl group present as part of thehigher fatty acid acyl radical. This would not be true if oleic acid,stearlc acid, linoleic acid, naphthenic acid, or the like, wereemployed. On the other hand, one could employ monoolein, di-olein,monostearin, di-stearin, mononaphthenin, di-naphthenin, etc. Likewise,one may employ a m chaas monp-ricinolein, di-ricinolein, and the like.Furthermore, in addition to employing such materials as ricinoleic acid,one may employ ethyl ricinoleate, ethylene glycol ricinoleate,tri-ricinoleate, etc.

Having prepared the 'polygylcol ethers of various polyhydroxylatedalkanes and polyhydric phenols, as previously described, a convenientsecond step in the preparation of the new composition of matter is toproduce acid esters of the kind obtainable between polybasic carboxyacids, or their functional equivalents, such as the anhydrides,-andhydroxylated fatty acids, esters, or the like.

Reference is made to the following examples which are indicated bystructural formulas and 7 described in detail in U. S. Patent No.2,166,432, dated July 18, 1939, to De Groote:

OOOH

COO.R.COO.CH1

OH.R.CO0. E

OILR-COO. HI

COOK

COO.R.COO.ZH2

HO.B.COO. H

coon

hooo-O-coonoomln 000011.000. n,

COOH

COOH

GOO.R.COO.({3HI COO.R.COO.GH

ooo.n.coo.cnl

Furthermore, note additional examples described in detail in U. S.Patent No. 2,166,433, dated July 18, 1939, to De Groote. Among thevarious examples are the following:

R.COO.C:HA

coon COOH COOK

(R.COO):CaIIrOOO OOOH 00C COOH 0H.R.COO.C:HI

00C OH.R.COO.C:HE

COOH

COOH

Pommssrc Rucrmrs Example 1 Polyphthalated triricinolein is prepared inthe 5 manner described in U. 8. Patent No. 1,976,602,

The previous examples exemplifying certain polycarboxylic reactants havebeen limited to the type in which phthalic anhydride was employed.Previously attention has been directed to the fact that numerous otherpolybasic acids or anhydrides, particularly maleic anhydrides, ad picacid, citraconic acid, azaleic acid, sebacic acid, succinic acid, etc.,might be employed just as advantageously,

dated October 9, 1934, to De Groote et al. (See page 4, lines 15 etseq.)

PoLYBAsIc Rnllcmn'rs Example 2 POLYBASIC REACTANIS Example 3Diphthalated mono-olein is prepared in a manner similar to the procedureemployed in preparing diphthalated diricinolein in Example 2,immediately preceding.

POLYBASIO RsAcrms Example 4 Dimaleated monostearin is prepared in amanner similar to that employed in the preceding examples.

POLYBASIC Rmcrmrs Example 5 Dioxalated monoabietin is prepared in a.manner similar to that employed in the precedin examples.

POLYBASIC RIACTAN'IS Example 6 Dicitrated mononaphthenin is prepared ina manner similar to that employed in the preceding examples.

POLYBASIC REACTANTS Example 7 1 mole of ricinoleic acid is reacted withone mole of phthalic anhydride.

POLYBASIO REACTANTS Example 8 1 mole of butyl ricinoleate is reactedwith 1 mole of phthallc anhydride.

FINAL COMPOSITION OF MATTER Example 1 1 pound mole of a hydroxylatedalkane, such as exemplified by Hydrophile Hydroxylated Alkanes, Examples1 to 'T, inclusive, is reacted with 1 mole of diphthalatedtriricinolein, so as to give a sub-resinous material in which there ispresent at least one unreacted carboxyl radical. The diphthalatedtriricinolein is, in turn, obtained by reaction between 1 mole oftriricinolein and two moles of phthaiic anhydride in the mannerpreviously described. The esteriflcation reactions are conducted in theusual manner (see, for example, U. S. Patent No. 2,166,433,aforementioned, page 6, right hand column, line 33).

FINAL Comosrrron or MATTER Example 2 FINAL Comrosmon or MATTER Emample 3The same procedure is followed as in Examples '1 and 2, preceding,except that materials of the kind exemplified by Polybasic Reactants,Ex-

amples 2 to 6, inclusive, are substituted for polyphthalatedtriricinolein.

Fmsr. Comrosrrrort or MATTER Example 4 The same procedure is followed asin the previous examples, except that Polybasic Reactants, Example 7 or8, are employed, followed by subsequent reaction with an additional moleof phthalic anhydrlde, or some other polybasic acid.

Attention is directed to what is perfectly obvious, in view of what hasbeen said previously, that an alternate method of obtaining thepreceding examples or kindred types, employs reactinga p lyglycol etherwith the polybasic acid, and then adding a selected detergent-formingmaterial, such as ricinoleic acid, methyl ricinoleate, triricinolein,mono-olein, or the like. Similarly, a somewhat different type isavalable by esterifying the polyglycol ether with the detergent-formingacid, and then reacting with the polybasic acid. Obviously, if all ofthe hydroxyls of the polyglycol ether are esterified with adetergent-forming monocarboxy acid, then at least one such high molalacyl radicals must contain a hydroxyl group. In other words, one shouldemploy a material of the type exemplified by ricinoleic acid,hydroxystearic acid, or the like. This then permits subsequent reactionwith a poly-basic acid, such as phthalic anhydride, or the like. If,however, the polyglycol-ether is esterified with oleic acid, naphthenicacid, oxidized petroleum acid, or abietic acid, then at least, oneunreacted hydroxyl group must be available for subsequent reaction withphthalic anhydride, or the like. In this connection, attention isdirected particularly to completion of the oxyalkylation reaction bymeans of glycld. For instance, where previous directions have called forthe use of 6 moles, or

12 moles, or 18 moles of ethylene oxide, it would be desirable to usesomewhat less. For instance, 4 moles, or 10 moles, or 16 moles, and thencomplete the oxyethylation by means of 2-moles of glycid.

We have found that the most suitable products for various purposes, andparticularly, for demulslflcation, are sub-resinous, semi-resinous, orbalsam-like products, and are preferably derived from polyfunctionalacylated reactants, in which the acyl group is derived from a high molaldetergent forming monocarboxy acid. We have found that such products aresoluble to a fairly definite state, for example, in some solvent, suchas water, alcohol, benzene, dichloroethyl ether, acetone, cresylic acid,dilute acidic acid, dioxane, or the like. This is simply another way ofstating that it is preferable, that the product be one of thesub-resins, which are commonly rethe use of the words acylation" islimited to high molal monocarboxy 10 1 ferred to as an A resin, or a Bresin, as distinguished from a C resin, which is a highly infusible,insoluble resin. (See Ellis, Chemistry of Synthetic Resins, 1935, page862, et seq.)

The hydroxylated products or acylated hydroxylated products, or thelike, may be considered as an alcohol, 1. e., a monohydric or polyhydricalcohol. If an alcohol is indicated by the formula Y (OHM where 11.indicates the number 1, or more, and if a polybasic acid body beindicated by the formula X(COOH), where n indicates the number 2, ormore, then the reaction between a monohydric alcohol and a polybasicacid will result in a compound which may be indicated by the followingformula: YX(COOH),.', where 71' indicates the number I, or more, andwhich is in reality a contraction of a more elaborate structuralformula, in which X and Y' are Joined by a carboxyl radical or residue.Assuming, however, as would be true in the majority of cam, that thealcohol actually would be a polyhydric alcohol, and that the acid bodywould be polybasic in nature, .for instance, if one employed adiphthalate of a polyhydroxylated ether or the like of the kindpreviously described, then examination reveals that the formula mightresult in a combination, in which there were neither residual carboxylradicals, nor residual hydroxyl radicals, or might result in compoundsin which there were residual hydroxyl radicals, and no residual carboxylradicals, or compounds where there might be residual carboxyl radicals,or compounds where there might be residual carboxyl radicals and noresidual hydroxyl radicals; or there might be both. This is indicated bythe following:

(Y.X)q(OH)m in which a indicates a small whole number (one in the caseof a monomer, and probably not over 10, and usually less than 5, and mand n indicate the number 1 Or more, and m" and n" indicate zero or asmall or moderately sized whole number, such as zero, one, or more, butin any event, probably a number not in excess of 4-8.

The words acidyl and acyl and the words "acidylation and acylation areusually used synonymously. Compounds of the type herein contemplated,and particularly for use as demulsifiers, are characterized by havingtwo different types of carboxylic acid radicals, or car: boxylic acylradicals present. One type is derived from high molal detergent-formingmonocarboxy acids, such as higher fatty acids, and the other type isderived from polybasic acids, particularly phthalic acid, and the like,or other suitable derivatives thereof, such as diethylphthalate. Forpurpose of clarity, in the hereto. attached claims, acyl, acylated" anddetergent-forming acids, whereas, the expressions acidyl, acidylated andacidylation are used in connection with polybasic carboxy acids.

Having thus described our invention, what we claim and desire to secureby Letters Patent is:

1. Sub-resinous polyesters having at least one free carboxyl radical, inwhich the radical derived from the alcohol of said sub-resinouspolyester is that of a di- (polyalkylene glycoxy) alkane in which theankenyl radical is selected from the group consisting of the aliphaticalkenyl radicals containing from 8 to 18 carbon atoms and thedicyclohexenyl dialkyl methanes in which each 75 alkyl radical containsless than 3 carbon atoms,

each polyalkylene glycoxy chain contains from 5 to 20 alkylene glycolradicals, and the alkylene radical is selected from the group consistingof ethylene and propylene, and the polycarboxy acid radical of saidsub-resinous polyester is that of a polycarboxy acidic fractional esterof a riclnolelc acid slyceride and has a plurality of tree carboxylradicals.

2. The sub-resinous ester, as defined in claim 1, with the proviso thatall polycarboxy acid radicals be dibasic.

3. The sub-resinous ester, as defined in claim 1, with the proviso thatall polycarboxy acid radicals be dibasic and the riclnolelc acidglyceride be triricinolein.

4. The sub-resinous ester, as defined in claim 1, with the proviso thatall polycarboxy acid radicals be phthalic acid radicals and thericlnolelc acid glyceride be triricinolein.

5. The sub-resinous ester, as defined in claim 1, with the proviso thatall polycarboxy acid radicals be maleic acid radicals and the ricinoleicacid glyceride be triricinolein.

6. The sub-resinous ester, as defined in claim 1, with the proviso thatall polycarboxy acid radicals be adipic acid radicals and the riclnolelcacid glyceride be triricinolein.

MELVIN DE GROOTE. BERNHARD KEISER.

